WO2002039184A1 - Materiaux d'enregistrement optique - Google Patents

Materiaux d'enregistrement optique Download PDF

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Publication number
WO2002039184A1
WO2002039184A1 PCT/GB2001/004978 GB0104978W WO0239184A1 WO 2002039184 A1 WO2002039184 A1 WO 2002039184A1 GB 0104978 W GB0104978 W GB 0104978W WO 0239184 A1 WO0239184 A1 WO 0239184A1
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WO
WIPO (PCT)
Prior art keywords
light
monomer
silicone
diffuser
mask
Prior art date
Application number
PCT/GB2001/004978
Other languages
English (en)
Inventor
Robin James Thomas Clabburn
Rifak Iqbal
Stephen Moratti
Original Assignee
Durand Technology Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB0027580A external-priority patent/GB0027580D0/en
Priority claimed from GB0029403A external-priority patent/GB0029403D0/en
Priority claimed from GB0109809A external-priority patent/GB0109809D0/en
Application filed by Durand Technology Limited filed Critical Durand Technology Limited
Priority to AU2002223792A priority Critical patent/AU2002223792A1/en
Publication of WO2002039184A1 publication Critical patent/WO2002039184A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/001—Phase modulating patterns, e.g. refractive index patterns
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/02—Alignment layer characterised by chemical composition
    • C09K2323/027—Polyimide
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H2260/00—Recording materials or recording processes
    • G03H2260/12—Photopolymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/117—Free radical

Definitions

  • THIS INVENTION relates to optical recording materials and to methods of forming optical devices such as diffiisers and holograms from such materials.
  • the present specification discloses, inter alia, various systems or mixtures of components which can be provided in the form of an extended layer and which are of such a character that when such an extended layer of such system or mixture is exposed to light or other appropriate radiation, at least some components of the system undergo polymerisation in the areas so exposed, whereby an end product is obtainable, (after any necessary processing steps), which comprises a solid, transparent, or at least light-transmitting sheet or layer characterised by refractive index variations and/or characterised by variations in layer thickness, i.e. by surface relief features.
  • Such systems are useful, for example as holographic recording materials, or in the production of microlens arrays, or of light-diffusing or de-pixelating screens.
  • known systems for the purpose referred to comprise a monomer or monomers capable of undergoing free-radical-initiated polymerisation, a photo- initiator capable of generating free radicals on exposure to radiation of the required wavelengths and a polymeric matrix or binder.
  • a monomer or monomers capable of undergoing free-radical-initiated polymerisation a photo- initiator capable of generating free radicals on exposure to radiation of the required wavelengths
  • a polymeric matrix or binder examples of such known systems or mixtures are disclosed in for example U.S. Patent Nos. 5470662, 4963471, 4942112, 3658526. It is among the objects of the present invention to provide an improved photopolymerisable system or mixture.
  • a photopolymerisable system capable of polymerisation to form a solid, light-transmitting material having volume refractive index variations and/or surface relief features dependent on the exposure of the system to polymerising radiation, wherein the system includes a silicone acrylic compound or compounds.
  • a system capable of being modified by electromagnetic radiation to provide a transparent or substantially transparent material having volume refractive index variations, or surface contour features, determined by exposure of the system to such radiation, the system comprising:-
  • the system may additionally include a compatible polymer, e.g. polymers or copolymers with similar groups to the silicone prepolymer.
  • a compatible polymer e.g. polymers or copolymers with similar groups to the silicone prepolymer.
  • Compatible polymers include PVA, polysiloxane polymers or acrylic type polymers such as PMMA. It is another object of the invention to provide an improved light-modifying structure using a system or mixture in accordance with the above noted aspect as a starting material.
  • a diffuser, hologram or other light-modifying structure formed by polymerisation of a system in accordance with the previously noted aspects of the invention.
  • a method of making a light-diffusing material comprising providing a photopolymerisable system capable of polymerisation to form a solid, light-transmitting material having volume refractive index variations and/or surface relief features dependent on the exposure of the system to polymerising radiation, and which method comprises exposing a layer provided by said system to polymerising radiation through an optical aperture screen to polymerise the material and subsequently polymerising any of the material still unpolymerised
  • a method of making a light-diffusing material comprising providing a photopolymerisable system capable of polymerisation to form a solid, light-transmitting material having volume refractive index variations and/or surface relief features dependent on the exposure of the system to polymerising radiation, and which method comprises exposing a layer provided by said system to polymerising radiation without any intervening mask and without other means of producing small scale variation of light intensity with position in the layer.
  • said system includes a silicone acrylate or similar compound or compounds.
  • the polymerising radiation is preferably parallel (collimated) or substantially parallel radiation.
  • the system comprises:-
  • component (b) which may be used include :-
  • Ebecryl 2047 (Trifunctional acrylate) RI - 1.4757 Genomer 4302 (Aliphatic Polyester Triurethane Triacrylate, hazardous component being urethane acrylate 100%) RI - 1.509
  • Photomer 4810 F (Ester of acrylic acid and isoCIO alcohol) or Isodecyl (IDA)
  • Genomer 4269/M22 (aliphatic difunctional urethane acrylate diluted in Genomer
  • TMPTA Trimethylopropane triacrylate
  • N-vinyl pyrrolidinone NVP
  • the system may additionally include a compatible polymer, e.g. polymers or copolymers with similar groups to the silicone prepolymer.
  • a compatible polymer e.g. polymers or copolymers with similar groups to the silicone prepolymer.
  • Compatible polymers or binders which may be used include PVA, polysiloxane polymers or acrylic-type polymers such as PMMA.
  • the formulation may include:- BLNDERS PVA MW 12800 PVA MW 10-15000 PMMA MW 3300 - 996000
  • silicone acrylate and monomer blends i.e. silicone acrylate and monomer blends; silicone acrylate or silicone methacrylate alone; silicone/acrylate monomer blends
  • various other components such as flexibilisers, binders, other monomers, stabilisers, defoamers, antioxidants, photoinitiators and amine synergists.
  • Poly(ethylene glycol)methyl ether (average Mn ca. 5,000,T m 52°)
  • Photomer 481 OF (Ester of acrylic acid and isoCIO alcohol) or Isodecyl (IDA)
  • Irgacure 184 (1-hydroxycyclohexylphenylketone)
  • Irgacure 369 (2-benzyl-2-(dimethyla ⁇ no)-4'-morpholino-butyrophenone
  • Speedcure ITX (a mixture of 2-isopropylthioxanthanone and 4- isopropylthioxanthanone - a Type II initiator which requires an amine synergist)
  • Actilane 800 is a silicone difunctional acrylate product from Akros Chemicals Ltd., Manchester; Daracure 1173 is 2-hydroxy-2- methyl- 1 -phenyl- 1-propanone: NVP is N-vinyl pyrrolidinone; PVA is poly(vinyl acetate) MW 12,800; TMPTA is trimethylolpropane triacrylate; POEA is 2-phenoxyethyl acrylate; Rahn 99-662 is a silicone acrylate a product from RAHN AG, Switzerland.
  • the Actilane 800 and Rahn 99-622 materials referred to are examples of materials referred to generally as silicone acrylates, and are also known as acrylate terminated poly (dimethylsiloxanes) (PDMS). Silicone acrylates useful in the context of the invention may also include alkane aliphatic, phenyl, other aromatic or cyclic groups, or vinyl groups in addition to or as an alternative to methyl groups.
  • silicone copolymers such as silicone methylaciylates or silicone acrylamide and silicone epoxy pre-polymers may be used instead of the silicone acrylate prepolymers referred to herein.
  • Figure l is a graph showing, for various diffusers according to the invention, variation of luminance with angle (theta) of observation (on one side of the diffuser) from the axis of incidence of a collimated beam directed normally onto the diffuser from the opposite side thereof,
  • Figure 2 shows micrographs of sections (perpendicular to the major plane of the photopolymerised layer), through a diffuser in accordance with the invention
  • Figure 3 is a schematic diagram, in vertical section through the photopolymer layer, illustrating one method of UV exposure in accordance with the invention
  • Figure 4 is a diagram similar to Figure 3 but illustrating another method in accordance with the invention.
  • Figures 5A and 5B are angle-of-view graphs for sample diffusers
  • Figure 6 is a schematic diagram of an apparatus used for forming holograms for text purposes in some of the examples herein,
  • Figure 7 is a schematic diagram illustrating the organisation of a commercial production line utilising the invention
  • Figures 8, 9 and 10 illustrate schematically different forms of coater arrangement which may be used in the final stage of the production line of Figure 7
  • Figure 11 shows structural chemical formulae for various materials referred to in the description below.
  • a light- ⁇ ffusing screen for use as a rear projection screen or a depixelating screen, is made by a technique similar to that disclosed in European Patent No. 0294122 or European Patent No. 0530269, and in which technique, a layer of photopolymerisable material is applied to an optical mask featuring a plurality of light-transmitting apertures or windows in an opaque background or a plurality of opaque spots or patches in a light-fransn ⁇ tting background, these apertures or patches being on a microscopic scale (typically about 2 microns, and up to about 10 microns maximum dimension).
  • optical diffusers using masks substantially of the kind disclosed in EP-0801767.
  • the mask took the form of a photographic negative or transparency in the conventional form of a glass plate bearing on one side a gelatine layer inco orating opaque silver grains.
  • the photopolymerisable mixture or system was coated directly onto the gelatine side of the prepared mask.
  • optical diffusers are manufactured by a process which is similar but in which no mask is used, the photopolymerisable mixture or system being coated directly onto a plain, transparent sheet or film.
  • a border or "frame” of plastics film defininig a central aperture to receive the polymerisable material was placed on the glass tile or optical mask. Having stirred the polymerisable formulation, a sufficient quantity was placed in the well, defined by said aperture, taking care to avoid bubbles as far as possible.
  • a piece of Mylar (R.T.M.) (polyester) with a release coating was placed over the top, taking care to place the side with the release coating facing the quantity of the formulation and a roller was passed over the top of the assembly to allow the formulation to spread out evenly filling the well within the template.
  • the tile or mask with the mylar side down was placed in an ultra-violet Ught exposure apparatus under a source of ultra-violet light for a standard period, (e.g. two minutes).
  • a standard period e.g. two minutes.
  • the photopolymerisable material was first exposed through the mask (a "contact printing” technique).
  • the tile or plate was then turned turned over and similarly exposed for a further period to provide a "blanket” exposure.
  • the film was then carefully separated from the glass or mask, Mylar and template, for optical testing and evaluation.
  • optical density of the mask was typically 1.6.
  • Optical density is defined in accordance with the following equation: -
  • transmittance is the proportion of the light striking the mask which is allowed to pass through it and OD is the optical density.
  • An optical density of 1.6 allows about 3% of the light to pass through.
  • Table 1 below sets out, for each of a plurality of trials, the respective formulation in accordance with the invention, (the components of each formulation or system being set out under the heading “Formulation”), the portions of the respective components, (these being set out in the column headed “Parts” in the same sequence as set out in the column “Formulation”), the optical density of each mask being set out in the column headed "Mask” and the characteristics of the resulting diffuser being summarised in the column headed "Comments”.
  • the characters in the brackets in the first column are codes identifying the particular system of formulation concerned. These codes are used to identify the respective formulations in the discussion below.
  • the indications "SURFACE RELIEF” and “VOLUME EFFECT” indicate respectively that the light-diffusive effect appeared to be entirely or almost entirely due to surface relief produced in accordance with the mask pattern, and that at least a significant part of the light-diffusing effect appeared to be due to refractive index variations within the bulk of the photopolymer layer.
  • Whether the light-diffusing effect was due to surface relief or to refractive index variations in the volume of the photopolymer layer was assessed by application of an index matching fluid such as propan-2-ol to the free surface of the photopolymer. If such application of propan-2-ol removed the light- diffusive effect, the diffusion was considered to be due to surface relief, whereas if it did not, the diffusion was considered to be due to refractive index variations in the volume of the material.
  • the photopolymerisation of some of the systems in accordance with the present invention is believed to be somewhat complex, in that it is believed that significant copolymerisation with the monomeric components (such as the NVP, POEA or TMPTA, etc. (also illustrated in Figure 11)), takes place and quite possibly a degree of crosslinking between the monomers (TMPTA, etc., ) and the silicone acrylate and even between these and the PVA (where present).
  • the monomeric components such as the NVP, POEA or TMPTA, etc. (also illustrated in Figure 11)
  • the PVA incorporated in some of the formulations indicated is added in order to increase the viscosity of the system, to assist in handling and processing of the coated masks, and to improve the mechanical properties of the end product, by improving flexibility etc., the PVA being effectively dissolved in the monomer and polymer. It is believed however, that during the UV curing described, some (beneficial) chemistry involving the PVA may also take place, including bonding or cross-linking with the monomer and/or with the functional groups of the silicone acrylate.
  • the alternatives to PVA noted herein by way of further compatible polymers likewise serve to increase viscosity of the uncured system and to improve flexibility in the end product.
  • Formulation MCL 63 (Actilane 800 with NVP) forms a diffuser that exhibits surface relief.
  • PVA as in Formulation MCL 65
  • the use of a cross-linker such as TMPTA with the Actilane 800 as in Formulation MCL 70 forms a diffuser that exhibits volume graded refractive index effects, i.e. a diffuser in which within the photopolymer material, the refractive index varies from position to position.
  • the addition of PVA as in Formulation MCL 73 does not change this result.
  • This particular formulation (MCL 73) formed a very hard film. The mixture was very viscous before being UV-cured.
  • Rahn 99-622 forms with TMPTA (MCL 76), POEA (MCL 77) or NVP (MCL 78) a diffuser that exhibits bulk- refractive index variation effects.
  • Variant systems may include PVA and a compatible organic solvent.
  • a further option would be to use poly(vinyl formal) or poly(vinyl butyral) (PVB) to improve refractive index modulation.
  • the combination of Rahn 99-622 with NVP and TMPTA (MCL 82) forms a diffuser that relies mainly on surface relief.
  • NVP and POEA (MCL 83) a diffuser is produced which exhibits volume refractive index variations.
  • the combination of Rahn 99-622, TMPTA and PVA (MCL 85) formed a surface relief diffuser that did not stick to the gelatine. It would be interesting to examine the addition of NVP and POEA to formulation MCL 85.
  • the photopolymerisable system or formulation was coated directly onto the gelatine surface of a photographic negative or transparency, it should be understood that in many cases, for example, where a holographic recording material is to be supplied to end users, the recording material may comprise a product in the form of the photopolymerisable system or formulation in accordance with the invention sandwiched between a relatively inert and ideally transparent sheet, for example, sandwiched between two sheets of Mylar (polyester) fihn.
  • Such a product may be made, for example, by modifying a formulation such as indicated by MCL 73 or MCL 85 in Table 1, by increasing the proportion of PVA and including a compatible solvent for the PVA (such as MEK), to provide a formulation of a viscosity low enough to allow it to be readily applied as a coating, and coating the fluid system onto one Mylar fihn in a coating apparatus, known per se, for applying a coating of uniform thickness, the second Mylar film subsequently being applied to the exposed surface of the photopolymerisable layer.
  • a formulation such as indicated by MCL 73 or MCL 85 in Table 1
  • a compatible solvent for the PVA such as MEK
  • Table 2 sets out refractive indices of the components of the formulations to which Table 1 relates.
  • Figure 1 shows angle of view characteristics for formulations MCL 76 and MCL 77 of about 10 and 16 degrees respectively.
  • Angle of View for a light-tians ⁇ ting light diffusing sheet is typically measured by directing a collimated light beam onto the sheet from one side and measuring, on the opposite side of the sheet, the intensity of the light emanating from the sheet over a range of angles with respect to the collimated beam.
  • the Angle of View in such a scenario is defined as the included angle over which the light intensity thus measured is 50% or more of the peak intensity so measured.
  • Low angle of view materials of this type typically do not exhibit Gaussian optical characteristics and the "see through" peak is ignored.
  • Figure 2 shows microtomed sections of a diffuser, (produced by photopolymerisation of MCL 76 through an aperture optical mask as described above), under high magnification (the thickness of the photopolymer film is about 100 microns). Graded refractive index optical structures extending perpendicular to the major faces of the film are clearly visible.
  • Table 3 sets out Angle of View data for diffusers manufactured as described above using the formulations and masks indicated in Table 1.
  • the Actilane 800 material and the Rahn 99-622 material referred to above, (and the Rahn 00-225 material referred to below), are prepolymers or macromonomers comprising molecules of significant molecular weight comprising a plurality of acrylic and siloxane groups, the molecules typically comprising an inorganic silicone backbone with pendant methyl groups. These materials, in the presence of free radicals, are able to undergo still further polymerisation. More particularly, these materials may comprise solutions of said prepolymers or macromonomers in further compatible monomers.
  • the NVP, TMPTA and POEA referred to are ethylenically unsaturated monomers capable of polymerisation in the presence of free radicals.
  • the Daracure 1173 (2-hydroxy-2-methyl-l -phenyl- 1-propanone) is a photoinitiator capable of generating free radicals when exposed to UV light, to bring about polymerisation of the silicone acrylate materials and the ethylenically unsaturated monomers.
  • an oxygen inhibitor or anti-oxidant in the formulation to improve shelf life and /or to ⁇ nimise interference by atmospheric oxygen in the polymerisation of the material whilst it is exposed to atmosphere during exposure to UV light.
  • the photopolymerisable material was exposed through an optical mask to produce the desired light diffusing sheets
  • the applicants have found that in certain conditions, at least some of the formulations noted, such as MCL 76 and MCL 77, will form a light diffusing layer when exposed to UV light even in the absence of an optical aperture mask of the kind described, eg. if the method described above is carried out except that the photopolymerisable material is coated directly onto a plain transparent glass plate instead of onto a photographic mask plate of the kind referred to.
  • Tables 4, 5 and 6 below provide angle of view results for a number of different photopolymerisable mixtmes or systems of various formulations and for two cases, namely (a) for exposure to collimated ultraviolet light through an aperture mask or screen, in the manner described with reference to Tables 1 to 3 above and (b) for exposure directly to collimated ultraviolet light distributed substantially uniformly over the plate or sample concerned, without any intervening photo mask, i.e. with the photopolymerisable material coated directly onto a plain transparent plate of glass or other transparent support.
  • the ultraviolet light was directed normal to, i.e. perpendicular to, the plane of the glass plate or other transparent support.
  • the exposure time comprised two substantially equal periods of exposure, one from the glass side of the photopolymerisable layer/glass plate combination and one from the opposite side of said combination.
  • the exposure was selected in accordance with the density of the optical mask to achieve the optimum angle of view and the technique was in general as described above in relation to Tables 1 to 3.
  • the numbers in the first horizontal row are identification numbers for the formulations concerned, and the numbers in the six horizontal rows below are the parts (by weight) in the respective formulation, of the components (e.g. Actilane 800; Daracure 1173; NVP; POEA; TMPTA and PVA) indicated in the column at the left of the table.
  • the components e.g. Actilane 800; Daracure 1173; NVP; POEA; TMPTA and PVA
  • the angle of view indicated is the mean angle of view, effectively the mean of the angle of view measured in one arbitrarily selected plane containing the axis of the incident beam illuminating the sample and the angle of view measured in a plane, likewise containing the axis of said incident beam and perpendicular to said arbitrarily selected plane.
  • Formulation 98 101 104 107 110 119 121 122 Actilane 800 60 60 60 60 60 75 60 60 Daracure 1173 5 4 4 4 5 5 5 5 NVP 40 40 40 20 40 25 50 25 POEA 40 20 20 40 40 50 50 50 TMPTA 10 10 5 10 10 25 19 15 PVA 10 10 10 15 15 15 15 20
  • Table 6 takes the same form as Tables 4 and 5 and illustrates corresponding results for formulations identified as 100 and 109, incorporating Crodamer UVS 500 resin (see below), instead of Actilane 800 or Rahn 99-622.
  • Formulation 100 corresponded with formulation 98 (Table 4) but with the Actilane 800 replaced by Crodamer UVS 500 and likewise corresponded with formulation 99 (Table 5) but with the Rahn 99 - 622 material replaced by Crodamer UVS 500.
  • Formulation 109 corresponded with formulation 107 (Table 4) but with the Actilane 800 replaced by Crodamer UVS 500, and corresponded with formulation 108 (Table 5) but with the Rahn 99 - 622 material replaced by Crodamer UVS 500.
  • Crodamer UVS 500 is a silicone acrylate resin available from Croda Resins Limited of Kent, England.
  • Figures 5A and 5B are angle-of-view graphs for samples produced from formulation 107, as described above respectively with an optical mask (Figure 5 A) and without any mask ( Figure 5B).
  • Figure 5A and Figure 5B comprises two plots, one (ref. "0 deg") of relative intensity with angle in one plane including the axis of the beam incident on the sample and the other (ref. "90 deg") of relative intensity with angle in a plane perpendicular to said one plane and including the axis of he beam incident on the sample. In each case, the incident beam was substantially normal to the plane of the sample.
  • the photopolymerisable materials may be exposed directly to photopolymerising coherent radiation using the photopolymerisable material to record a holographic image directly and produce a volume or phase hologram.
  • a hologram may first be recorded, in coherent light, on a photographic film or plate which is subsequently developed and used as a mask through which a layer of such photopolymer is exposed to polymerising radiation in substantially the same way as described above for the manufacture of a diffuser using a mask, but the result is not a true volume hologram and, of course, the latter method would involve an additional, and generally unnecessary method step).
  • an argon laser 200 was set up as shown in Figure 6 to enable samples of photopolymer to be exposed to UV light.
  • the laser operated at about 350 nm at an output power of 300 mwatt.
  • a drop of photopolymer material 199 was placed on a microscope slide 201 then covered with a circular cover slide 203 about 23 mm in diameter. This produced samples between 30 and 70 microns thick.
  • Light from the laser 200 was directed onto a concave mirror 202 and directed therefrom, as an expanding beam, onto a glass prism 204 arranged as indicated.
  • the prism had the form of an isosceles triangle with its based parallel with and directly above the slide 201/layerl99/cover 203 sandwich and with the prism located centrally in the laser beam from mirror 202 (which beam was directed substantially along the normal to the planes of the interfaces between the layer 199 and the microscope slide and cover slip.
  • the use of the prism 204 produced an interference pattern (hologram) within the photopolymer and the energy in the UV light caused the photopolymer to polymerise to a solid film.
  • the exposure time was typically 30 seconds and increasing the exposure to 120 seconds did not appear to affect the quality of the hologram.
  • the hologram could be replayed by using sunlight or a similar bright source.
  • Tables 7 and 8 The formulations evaluated are set out in Tables 7 and 8 below.
  • each formulation or system is set out in the second to sixth row in the column which is furthest to the left, whilst the first row in each table carries a series of numerical identifiers or codes, each representing a particular formulation or system.
  • the column directly below each such identifier or code sets out, in the second to sixth row, the proportions, in the respective formulation or system, of the respective component in the same row in the column which is furthest to the left .
  • Variant systems may include PVA and a compatible organic solvent.
  • a further option would be to use poly(vinyl formal) or poly(vinyl butyral) (PVB) to improve refractive index modulation.
  • Tables 7 and 8 show in the penultimate row in the table (AOV mask) the angle of view of the diffuser resulting from such exposure of the respective material samples through such an aperture mask and in the last row (No mask) the angle of view of the diffuser resulting from such exposure of the respective material samples directly, without such a mask.
  • Formulations 211, 212 and 213 are respectively 100 pts of the respective above resin indicated in Table C plus three parts of photoinitiator (Daracure 1173).
  • haze in Table 9 it should be noted that with very weak diffusers it is possible to differentiate between such haze and the diffusing characteristics of a diffuser with light guiding structures by observing off-axis transmission. Haze increases with the extent to which the incident radiation is off- axis as compared with on axis because haze is thickness dependent. Materials incorporating light guiding structures become more transparent off-axis.
  • the silicone acrylate resins used were: Actilane 800, Rahn 00-225 and Rahn 99- 622.
  • Rahn 99-622 contains the same resin as Rahn 00-225 but has been diluted with polyether polyol terra acrylate (PPTTA) in the ratio of 30:70. (PPTTA:Rahn 00-225). Rahn 00-225 is very viscous, more viscous than Actilane 800 and apparent of higher MW.
  • PPTTA polyether polyol terra acrylate
  • PVA may be added to Actilane 800 as in Table 8.
  • a cross-linker such as TMPTA with the Actilane 800 as in Table 8 or with Rahn 00-225 as in Table 7 encourages volume graded refractive index effects, i.e. the refractive index varies from position to position within the photopolymer material.
  • the addition of PVA does not change this result.
  • silicone acrylate resins have the ability to form diffusers when an aperture mask is used and to some extent without, provided the viscosity is sufficiently low to allow diffusion during the exposure process.
  • the presence of the PPTTA monomer in MCL 213 illustrates this and the difference between 211 and 213 suggests the importance of molecular weight (MW). From these results it can be seen that the combination of silicone (or siloxane) resin and acrylic (or methacrylate) monomer in appropriate proportions could be used to create both diffusers and holograms.
  • the recording material may comprise a product in the form of the photopolymerisable system or formulation in accordance with the invention sandwiched between a relatively inert and ideally transparent sheet, for example, sandwiched between two sheets of Mylar (polyester) film.
  • Such a product may be made, for example, by modifying the formulations indicated in Table 7 and Table 8 by increasing the proportion of PVA and including a compatible solvent for the PVA (such as MEK), to provide a formulation of a viscosity low enough to allow it to be readily applied as a coating, and coating the fluid system onto one Mylar film in a coating apparatus, known per se, for applying a coating of uniform thickness, the second Mylar film subsequently being applied to the exposed surface of the photopolymerisable layer after removal of excess solvent from the coating.
  • a compatible solvent for the PVA such as MEK
  • FIG. 7 illustrates schematically a production line for holographic material (or material for producing diffusers) of the kinds referred to herein.
  • the individual components of the photopolymerisable system are supplied from bulk storage 100 by suitable metering means 102, (ensuring the correct proportions of the components), to a mixing facility 104, known per se, from whence the mixture is pumped by a pump to a coater 108.
  • Figures 8, 9 and 10 illustrate schematically different coater arrangements may be used.
  • an endless flexible web or conveyor belt 110 is coated directly, on its upper rub, with the photopolymerisable mixture by coater 108 and carries the coating thereon to an exposure station 112 where a nitrogen blanket is maintained over the coating once it is exposed to, for example, coherent UV Ught from source 114, forming a holographic image, (or such as to form an optical diffuser), and after the resulting polymerisation and curing, the polymerised material, now forming a solid flexible, self-supporting fi m 116, is stripped from the conveyor and wound up on a take-up reel 118, with a protective film 120 which lies between successive turns of the polymerised product.
  • Figure 9 differs from that of Figure 8 in that the photopolymerisable material is coated onto a polyester film 124 drawn from a reel 126 and supported by the conveyor, the coated polyester film 128 being wound up on a take-up reel 118 with a protective film 120 being again interleaved between successive turns of the product on the take-up reel.
  • FIG. 10 corresponds with that of Figure 9 except that, directly after coating the polyester film on the conveyor, and before exposure, a further transparent fihn 140, (which may also be polyester), is appUed on top of the coating.
  • the further film 140 on top of the coating serves to exclude air from the photopolymerisable coating, no nitrogen gas blanket needs to be employed.
  • the top film 140 is peeled off from the photopolymer around a roller 142 and the product is wound onto a take-up reel 118. (It may be possible to re-use the top film 140).
  • the substrate 124, with the cured coating thereon, is then wound onto a take-up reel as before, with an interleaved protective layer. Substantially the same arrangements can be used whether the end product comprises phase holograms or optical diffusers.
  • test samples were prepared either using a commercially available laminator or using the "screen printing technique" described above.
  • Section A and Section B respectively set out results for tests conducted using the formulations indicated (where the nature of the materials Rahn 99-622, Actilane 800, Daracure 1173 etc. were as set out earlier in this specification).
  • the first row in each table referenced MCL in the left hand column, carries, as headings, identification numbers for each formulation, to which the column below relates.
  • the last row in each table sets out the angle of view in each of two orhthogonal directions for the respective example exposed without an optical mask; the second from last row in each table sets out the exposure time for each sample, both for the example exposed without a mask and for the example exposed through a mask and for which the angles of view in each of two orthogonal diUections are set out in the third from last row.
  • Section A The samples in Section A were UV-cured on an apparatus termed, for convenience, the 'Elephant' (which has an ultra- violet source which produces weU collimated UV light.) at 650 w @ 4.5min/m for formulations MCL 176, 208, 295 and 1000 W for formulation MCL 188.
  • the 'Elephant' which has an ultra- violet source which produces weU collimated UV light.
  • Section B the samples were prepared by hand using the screen printing technique referred to above with a template of known thickness (100-150 microns) on a glass plate or photographic plate/mask then UV-cured on the 'Elephant' .
  • Rahn 99-622 is a combination of Rahn 00-225 (30%) and PPTTA (70%).
  • the chemical PPTTA, tradename Genomer 1456 is polyetherpolyoltetraacrylate
  • Ebecryl 1360 and 350 are from UCB Chemicals Limited CN 990 is from Sartomer Perenol S71 UV is from Cognis
  • silicone acrylate prepolymers as described above include siloxane and acrylic monomers and prepolymers incorporated as separate components and the acrylate components replaced by methacrylates or acrylamides or other reactive species such as epoxies or polyesters and incorporating the appropriate polymerisation initiators.
  • the thickness of the photopolymorisable layer exposed to form a diffuser in the manner described is of some importance, insofar as they have found that, below a certain thickness, a given formulation, at least where exposed without a mask, fails to form a diffuser. This critical thickness, it has been found, is different for different formulations. Furthermore the appUcants have noted that increases in thickness alter the light diffusing properties of the diffuser produced little, or not at all. With these factors in mind, it is possible by a few simple tests to establish the optimum thickness for each system formulation.
  • the silicone content of the photopolymerisable formulation used is calculated as the weight, in the total formulation of the
  • the silicone content of the formulation should be between 15 and 90%, preferably between 25 and 80% and most preferably between 30 and 60% of the reactive components.
  • the light or other radiation used should be collimated, i.e. substantially parallel.
  • useful diffusers can be produced using UV light which is less than perfectly collimated, e.g.
  • ⁇ is preferably less than 10 % more preferably less than 5°, although for some applications it may be necessary for ⁇ to be less than 1°.
  • the 'Elephant' is an apparatus for exposing photopolymerisable samples prepared as described herein and which directs a closely collimated beam of UV light (within 1° of perfect parallelism) onto the sample.
  • the 'Natgraph' (UV source where the degree of collimation can be varied) is an apparatus for the same purpose which provides light collimated only to within 5° of perfect parallelism. Table 13 illustrates the significance of the degree of collimation afforded by these two apparatuses.
  • optical diffusers manufactured in accordance with the invention have, in many cases, the curious property that if viewed at an angle significantly displaced from the original angle of incidence of the polymerising radiation on the precursor material the diffuser appears substantially clear transparent whilst if viewed in a direction aligned with the direction of incidence of the original polymerising radiation on the precursor material, the diffuser appears as a normal light diffuser.
  • the references in the table above to "clear when twisted” referred to this phenomenon. appears as a normal light diffuser.
  • the references in the table above to "clear when twisted” referred to this phenomenon.
  • the materials disclosed above may be used, inter alia, in the manufacture of holograms, microlens arrays, and of light-diffusing or depixelating screens by the techniques disclosed above.
  • Diffusers made using the materials of the invention by the above-described methods in accordance with the invention, have the useful property of being polarisation maintaining, and , indeed have polarisation maintenance typically better than 97%. That is to say, if, for example, light passing through such a diffuser is 100% plane polarised with a particular direction of polarisation before reaching the diffuser, 97% or more of the light emerging from the diffuser wiU still be plane polarised in the same direction. This has significant implications for the use of such diffusers in conjunction with LCD displays, for example, which rely upon control of polarisation of light to produce visible text and graphics
  • optical diffusers by either the mask exposure method or the maskless exposure method discussed above, which have better than 99% polarisation maintenance.
  • optical diffusers produced by exposure of commercially available photopolymers through optical aperture masks have, at best, had around 97% polarisation maintenance.
  • optical diffusers may be produced using the silicone based materials of the invention (and again by either the mask exposure method or the maskless exposure method), having an angle of view as high as 56 degrees, whereas the greatest angle of view that has until now be achievable by exposure of commercially available photopoloymers through optical masks, (necessary to achieve a diffuser in the case of such commercially available photopolymers), has been around 35 degrees, where surface relief effects have been removed or avoided, or 40 degrees taking advantage of surface relief effects. (In the case of optical diffusers manufactured in accordance with the present invention, the angle of view of up to 56 degrees is achievable without relying upon surface relief effects, i.e. by relying wholly upon refractive index variations within the volume of the diffuser material).
  • polymerisation as used herein, is intended to encompass processes by which homopolymers are formed as well as processes by which co-polymers are formed.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Holo Graphy (AREA)
  • Polymerisation Methods In General (AREA)
  • Optical Elements Other Than Lenses (AREA)

Abstract

L'invention concerne un système photopolymérisable que l'on peut polymériser par exposition à la lumière ultraviolette, par exemple, afin de former un matériau solide en feuille transmettant la lumière présentant des variations d'indice de réfraction volumique définissant un diffuseur optique ou un hologramme par exemple. Ce système comprend un monomère, un prépolymère, un macromonomère ou un co-monomère et un monomère éthyléniquement insaturé de silicone capable de subir une polymérisation initiée par un radical libre et comprend également un photoamorceur.
PCT/GB2001/004978 2000-11-10 2001-11-09 Materiaux d'enregistrement optique WO2002039184A1 (fr)

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AU2002223792A AU2002223792A1 (en) 2000-11-10 2001-11-09 Optical recording materials

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GB0027580A GB0027580D0 (en) 2000-11-10 2000-11-10 Improvements in or relating to optical recording materials
GB0027580.0 2000-11-10
GB0029403.3 2000-12-01
GB0029403A GB0029403D0 (en) 2000-12-01 2000-12-01 Improvements in or relating to optical recording materials
GB0109809.4 2001-04-20
GB0109809A GB0109809D0 (en) 2001-04-20 2001-04-20 Improvements in or relating to optical recording materials

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US20040219457A1 (en) 2004-11-04
AU2002223793A1 (en) 2002-05-21
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AU2002223792A1 (en) 2002-05-21
US7232651B2 (en) 2007-06-19
AU2002214143A1 (en) 2002-05-21
JP2004525394A (ja) 2004-08-19
EP1336131A1 (fr) 2003-08-20
JP2004526174A (ja) 2004-08-26
JP4535309B2 (ja) 2010-09-01
EP1344108B1 (fr) 2018-07-11
WO2002039183A1 (fr) 2002-05-16
EP1344108A1 (fr) 2003-09-17

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